JP7387790B2 - Glass compositions with low thermal expansion coefficients and glass fibers - Google Patents
Glass compositions with low thermal expansion coefficients and glass fibers Download PDFInfo
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- JP7387790B2 JP7387790B2 JP2022043898A JP2022043898A JP7387790B2 JP 7387790 B2 JP7387790 B2 JP 7387790B2 JP 2022043898 A JP2022043898 A JP 2022043898A JP 2022043898 A JP2022043898 A JP 2022043898A JP 7387790 B2 JP7387790 B2 JP 7387790B2
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- 239000011521 glass Substances 0.000 title claims description 117
- 239000000203 mixture Substances 0.000 title claims description 117
- 239000003365 glass fiber Substances 0.000 title claims description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 51
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 35
- 239000005751 Copper oxide Substances 0.000 claims description 32
- 229910000431 copper oxide Inorganic materials 0.000 claims description 32
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 30
- 239000000395 magnesium oxide Substances 0.000 claims description 29
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 29
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 29
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 24
- 239000011787 zinc oxide Substances 0.000 claims description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 22
- 229910052810 boron oxide Inorganic materials 0.000 claims description 22
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000292 calcium oxide Substances 0.000 claims description 19
- 239000002019 doping agent Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 15
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 239000005357 flat glass Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 35
- 238000002844 melting Methods 0.000 description 24
- 230000008018 melting Effects 0.000 description 24
- 238000002156 mixing Methods 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 238000009987 spinning Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- -1 alkali metal salts Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
本発明は、ガラス組成物及びガラス繊維に関し、特に、低膨張係数を持つガラス組成物、及びガラス繊維に関するものである。 TECHNICAL FIELD The present invention relates to glass compositions and glass fibers, and particularly to glass compositions and glass fibers with low expansion coefficients.
ガラス繊維は、優れた電気絶縁性、低消耗性、及び高安定性などの利点を持つので、回路基板、光ファイバー通信、電子製品の外装ケースなどに広く応用されている。例えば、ガラス繊維をプリント基板に適用する場合は、金属箔シート／配線などの電子部品に貼り付けるための絶縁層又は絶縁部に補強材料として添加しており、熱膨張係数の違いによる絶縁層又は絶縁部と金属箔シート／配線との間の剥離の発生を抑制するために、低熱膨張係数（Ｃｏｅｆｆｉｃｉｅｎｔ ｏｆ ｔｈｅｒｍａｌ ｅｘｐａｎｓｉｏｎ，ＣＴＥ）を持つガラス繊維の研究開発が進められている。 Glass fiber has advantages such as excellent electrical insulation, low wear and tear, and high stability, so it is widely applied to circuit boards, optical fiber communications, external cases of electronic products, etc. For example, when glass fiber is applied to printed circuit boards, it is added as a reinforcing material to the insulating layer or insulating part to be attached to electronic components such as metal foil sheets/wirings, and the insulating layer or insulating part due to the difference in thermal expansion coefficient. In order to suppress the occurrence of peeling between the insulating portion and the metal foil sheet/wiring, research and development of glass fibers having a low coefficient of thermal expansion (CTE) is underway.
現在市販されている低熱膨張係数のガラス繊維は、熱膨張係数が約３ｐｐｍ／℃～４ｐｐｍ／℃の範囲にあるが、ハイテク産業の発展に伴い、配線パターンの設計も日々複雑化しており、製造過程における熱膨張や収縮などによる残留応力が電子部品に影響を与えてしまうため、業界では、より低い熱膨張係数を有するガラス繊維が求められている。 Glass fibers with a low coefficient of thermal expansion currently on the market have a coefficient of thermal expansion in the range of approximately 3 ppm/°C to 4 ppm/°C, but with the development of high-tech industry, the design of wiring patterns is becoming more complex day by day. The industry is looking for glass fibers with lower coefficients of thermal expansion, as residual stress due to thermal expansion and contraction during the process can affect electronic components.
このように、本発明は、低熱膨張係数を持つガラス組成物を提供することを目的としている。 Thus, the present invention aims to provide a glass composition with a low coefficient of thermal expansion.
上記目的を達成するために、本発明は、低熱膨張係数を持つガラス組成物であって、酸化ケイ素（ＳｉＯ２）、酸化アルミニウム（Ａｌ２Ｏ３）、酸化ホウ素（Ｂ２Ｏ３）、酸化マグネシウム（ＭｇＯ）、酸化カルシウム（ＣａＯ）、酸化亜鉛（ＺｎＯ）及び酸化銅（ＣｕＯ）を含むことを特徴とする。 In order to achieve the above object, the present invention provides a glass composition with a low coefficient of thermal expansion, comprising silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), boron oxide (B 2 O 3 ), It is characterized by containing magnesium (MgO), calcium oxide (CaO), zinc oxide (ZnO) and copper oxide (CuO).
尚、前記ガラス組成物の重量パーセント１００ｗｔ％に対して、該酸化ケイ素の含有量は５５ｗｔ％～６３ｗｔ％の範囲にあり、該酸化アルミニウムの含有量は１５ｗｔ％～２２ｗｔ％の範囲にあり、該酸化ホウ素の含有量は６ｗｔ％～１３ｗｔ％の範囲にあり、該酸化マグネシウムの含有量は５ｗｔ％～１４ｗｔ％の範囲にあり、該酸化カルシウムの含有量は０．１ｗｔ％～４ｗｔ％の範囲にあり、該酸化亜鉛の含有量は０ｗｔ％～８ｗｔ％の範囲にあり、該酸化銅の含有量は０．０３ｗｔ％～７ｗｔ％の範囲にあることを特徴とする。 In addition, with respect to 100 wt% of the weight percentage of the glass composition, the content of the silicon oxide is in the range of 55 wt% to 63 wt%, the content of the aluminum oxide is in the range of 15 wt% to 22 wt%, and the content of the aluminum oxide is in the range of 15 wt% to 22 wt%. The content of boron oxide is in the range of 6wt% to 13wt%, the content of magnesium oxide is in the range of 5wt% to 14wt%, and the content of calcium oxide is in the range of 0.1wt% to 4wt%. The zinc oxide content is in the range of 0 wt% to 8 wt%, and the copper oxide content is in the range of 0.03 wt% to 7 wt%.
また、本発明の他の目的は、低熱膨張係数を持つガラス繊維を提供することである。 Another object of the present invention is to provide a glass fiber with a low coefficient of thermal expansion.
上記目的を達成するために、本発明は、前述の低熱膨張係数を持つガラス組成物からなるガラス繊維であって、該ガラス繊維の熱膨張係数が３ｐｐｍ／℃以下であることを特徴とする。 In order to achieve the above object, the present invention provides a glass fiber made of the above-mentioned glass composition having a low coefficient of thermal expansion, characterized in that the coefficient of thermal expansion of the glass fiber is 3 ppm/°C or less.
本発明の異質な効果とは、本発明の低熱膨張係数を持つガラス組成物中の酸化銅の含有量を増加させ、酸化亜鉛の含有量を減少させることにより、当該低熱膨張係数を持つガラス組成物からなるガラス繊維の熱膨張係数を３ｐｐｍ／℃以下に低減させることにある。 The unique effect of the present invention is that by increasing the content of copper oxide and decreasing the content of zinc oxide in the glass composition with a low coefficient of thermal expansion of the present invention, the composition of the glass composition with a low coefficient of thermal expansion can be improved. The object of the present invention is to reduce the thermal expansion coefficient of glass fiber made of plastic to 3 ppm/°C or less.
本発明に係る低熱膨張係数を持つガラス組成物は、低熱膨張係数を持つガラス繊維を製造するために用いられる。概略的に説明すると、当該ガラス繊維は、本発明のガラス組成物を十分に混合した後、高温で溶融、紡糸などの工程を順次行うことにより製造され、熱膨張係数は３ｐｐｍ／℃以下である。 The glass composition with a low coefficient of thermal expansion according to the present invention is used to produce glass fibers with a low coefficient of thermal expansion. Briefly, the glass fiber is manufactured by thoroughly mixing the glass composition of the present invention and then sequentially performing steps such as melting and spinning at high temperature, and has a coefficient of thermal expansion of 3 ppm/°C or less. .
本発明のガラス組成物の一つの実施例においては、酸化ケイ素（ＳｉＯ２）、酸化アルミニウム（Ａｌ２Ｏ３）、酸化ホウ素（Ｂ２Ｏ３）、酸化マグネシウム（ＭｇＯ）、酸化カルシウム（ＣａＯ）、酸化亜鉛（ＺｎＯ）、酸化銅（ＣｕＯ）、及びドーパントを含む。 In one embodiment of the glass composition of the present invention, silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), boron oxide (B 2 O 3 ), magnesium oxide (MgO), calcium oxide (CaO) , zinc oxide (ZnO), copper oxide (CuO), and dopants.
具体的に述べると、前記ガラス組成物の重量パーセント１００ｗｔ％に対して、該酸化ケイ素の含有量は５５ｗｔ％～６３ｗｔ％の範囲にあり、該酸化アルミニウムの含有量は１５ｗｔ％～２２ｗｔ％の範囲にあり、該酸化ホウ素の含有量は６ｗｔ％～１３ｗｔ％の範囲にあり、該酸化マグネシウムの含有量は５ｗｔ％～１４ｗｔ％の範囲にあり、該酸化カルシウムの含有量は０．１ｗｔ％～４ｗｔ％の範囲にあり、該酸化亜鉛の含有量は０ｗｔ％～８ｗｔ％の範囲にあり、該酸化銅の含有量は０．０３ｗｔ％～７ｗｔ％の範囲にあり、該ドーパントの含有量は１．２ｗｔ％以下である。 Specifically, the content of silicon oxide is in the range of 55 wt% to 63 wt%, and the content of aluminum oxide is in the range of 15 wt% to 22 wt%, based on the weight percentage of the glass composition of 100 wt%. The content of boron oxide is in the range of 6wt% to 13wt%, the content of magnesium oxide is in the range of 5wt% to 14wt%, and the content of calcium oxide is in the range of 0.1wt% to 4wt%. %, the content of zinc oxide is in the range of 0 wt% to 8 wt%, the content of copper oxide is in the range of 0.03 wt% to 7 wt%, and the content of the dopant is 1. It is 2wt% or less.
本発明のガラス組成物における、酸化ケイ素、酸化アルミニウム及び酸化ホウ素は、前記ガラス繊維を構成する主成分であり、そのうち酸化ケイ素は、網目形成成分（Ｎｅｔｗｏｒｋ ｆｏｒｍｅｒ）であることから、その四面体の結晶格子構造［ＳｉＯ４］で連続した網目構造を形成して、本発明のガラス組成物からなるガラス繊維の主要な構造となる。酸化アルミニウムは、本発明のガラス組成物の中間体（ｉｎｔｅｒｍｅｄｉａｔｅ）となるものであり、酸化ケイ素における一部の酸素原子と結合して架橋酸素を形成して、該ガラス組成物の熱安定性及び粘度をさらに高めるために用いられるが、該酸化アルミニウムの含有量が多すぎると、当該ガラス組成物の粘度が高くなり、その後のガラス繊維の製造工程において、大量の加熱エネルギーを供給しなければならず、生産コストの増大を招いてしまう。酸化ホウ素は、四面体の結晶格子構造での酸化ケイ素と結合して、安定した連続構造を形成することができ、また、製造工程においての高温状態下では粘度を下げ、結晶析出を抑える作用があり、一方、製造工程においての低温状態下ではガラス構造の緊密度を向上させ、当該ガラス組成物の熱膨張係数を低下させることができるが、該酸化ホウ素の含有量が多すぎると、製造工程の高温状態で過度の蒸発が起こり、当該ガラス組成物の組成に変動が生じ、該ガラス組成物の電気絶縁性にも影響を及ぼしてしまう。 In the glass composition of the present invention, silicon oxide, aluminum oxide, and boron oxide are the main components constituting the glass fiber, and since silicon oxide is a network former, the tetrahedral The crystal lattice structure [SiO 4 ] forms a continuous network structure, which becomes the main structure of the glass fiber made of the glass composition of the present invention. Aluminum oxide serves as an intermediate for the glass composition of the present invention, and combines with some oxygen atoms in silicon oxide to form bridging oxygen, thereby improving the thermal stability of the glass composition. It is used to further increase the viscosity, but if the content of aluminum oxide is too large, the viscosity of the glass composition increases, and a large amount of heating energy must be supplied in the subsequent glass fiber manufacturing process. However, this leads to an increase in production costs. Boron oxide can combine with silicon oxide in a tetrahedral crystal lattice structure to form a stable continuous structure, and also has the effect of lowering viscosity and suppressing crystal precipitation under high temperature conditions during the manufacturing process. On the other hand, under low temperature conditions during the manufacturing process, the tightness of the glass structure can be improved and the coefficient of thermal expansion of the glass composition can be lowered, but if the content of boron oxide is too large, the manufacturing process Excessive evaporation occurs at high temperatures, causing fluctuations in the composition of the glass composition and affecting the electrical insulation properties of the glass composition.
本実施例においては、前記ガラス組成物の重量パーセント１００ｗｔ％に対して、前記酸化ケイ素の含有量は５５ｗｔ％～６３ｗｔ％の範囲にあり、前記酸化アルミニウムの含有量は１５ｗｔ％～２２ｗｔ％の範囲にあり、前記酸化ホウ素の含有量は６ｗｔ％～１３ｗｔ％の範囲にある。尚、該酸化ホウ素の含有量は、６ｗｔ％～１１ｗｔ％の範囲にあることが好ましく、また、該酸化ケイ素と酸化アルミニウムと酸化ホウ素の含有量の合計は、８４ｗｔ％～９０ｗｔ％の範囲にあることが好ましい。 In this example, the content of silicon oxide is in the range of 55 wt% to 63 wt%, and the content of aluminum oxide is in the range of 15 wt% to 22 wt% with respect to 100 wt% of the glass composition. The boron oxide content is in the range of 6wt% to 13wt%. The content of boron oxide is preferably in the range of 6 wt% to 11 wt%, and the total content of silicon oxide, aluminum oxide, and boron oxide is in the range of 84 wt% to 90 wt%. It is preferable.
酸化マグネシウム及び酸化カルシウムは、本発明のガラス組成物の高温時の粘度を適度に減少させることができるので、製造時における当該ガラス組成物の溶融を促進させるが、該酸化カルシウムの含有量が多すぎると、結晶析出現象が増えてしまい、この場合、酸化マグネシウムの添加は当該ガラス組成物の機械的強度を高めるのに役立つが、酸化マグネシウムの含有量が多すぎると、ガラス構造の緊密度が落ち、熱膨張係数の低減に不利となる。 Magnesium oxide and calcium oxide can moderately reduce the viscosity of the glass composition of the present invention at high temperatures, and therefore promote melting of the glass composition during production. If the content is too high, the crystal precipitation phenomenon will increase, and in this case, the addition of magnesium oxide will help increase the mechanical strength of the glass composition, but if the content of magnesium oxide is too high, the tightness of the glass structure will decrease. This is disadvantageous for reducing the coefficient of thermal expansion.
本実施例においては、前記ガラス組成物の重量パーセント１００ｗｔ％に対して、前記酸化マグネシウムの含有量は５ｗｔ％～１４ｗｔ％の範囲にあり、前記酸化カルシウムの含有量は０．１ｗｔ％～４ｗｔ％にある。尚、該酸化マグネシウムの含有量は５ｗｔ％～９．５ｗｔ％、該酸化カルシウムの含有量は０．１ｗｔ％～０．４ｗｔ％の範囲にあることが好ましい。 In this example, the content of magnesium oxide is in the range of 5 wt% to 14 wt%, and the content of calcium oxide is in the range of 0.1 wt% to 4 wt% with respect to 100 wt% of the glass composition. It is in. Note that the content of the magnesium oxide is preferably in the range of 5 wt% to 9.5 wt%, and the content of the calcium oxide is preferably in the range of 0.1 wt% to 0.4 wt%.
酸化亜鉛及び酸化銅の添加は、本発明に係るガラス繊維の熱膨張係数の低減に役立つものであり、本実施例においては、前記ガラス組成物の重量パーセント１００ｗｔ％に対して、該酸化亜鉛の含有量は０ｗｔ％～８ｗｔ％の範囲にあり、該酸化銅の含有量は０．０３ｗｔ％～７ｗｔ％の範囲にある。しかしながら、一般的なガラス組成物には、アルカリ金属塩類（例えば、酸化カリウム、酸化ナトリウムなど）も添加されるが、ガラス組成物がアルカリ金属塩類を含むと、酸化亜鉛の存在により、かえって当該ガラス組成物本来の緻密な構造が緩くなり、膨張係数の低減に不利となる。従って、一部の実施例においては、ガラス組成物がアルカリ金属塩類などの成分を含有する場合、必要に応じて酸化亜鉛を添加しなくてもよい。 The addition of zinc oxide and copper oxide helps to reduce the coefficient of thermal expansion of the glass fiber according to the present invention, and in this example, the addition of zinc oxide to 100 wt% of the glass composition is The content ranges from 0 wt% to 8 wt%, and the copper oxide content ranges from 0.03 wt% to 7 wt%. However, although alkali metal salts (e.g., potassium oxide, sodium oxide, etc.) are also added to general glass compositions, if the glass composition contains alkali metal salts, the presence of zinc oxide may cause the glass to become The originally dense structure of the composition becomes loose, which is disadvantageous to reducing the expansion coefficient. Therefore, in some embodiments, zinc oxide may not be optionally added when the glass composition contains components such as alkali metal salts.
本発明では、ガラス繊維の熱膨張係数をさらに下げるために酸化銅を添加することにより、当該ガラス繊維の熱膨張係数を低減させると共に、ガラス組成物は製造工程において緻密な構造を形成する傾向があり、酸化亜鉛によるガラス組成物の構造の粗雑化を抑制することができる。しかしながら、酸化銅の含有量が７ｗｔ％を超えると、生成されたガラス繊維中の結晶析出現象が増加する傾向にあり、その後の使用に不利となる。 In the present invention, by adding copper oxide to further lower the thermal expansion coefficient of the glass fiber, the thermal expansion coefficient of the glass fiber is reduced, and the glass composition tends to form a dense structure during the manufacturing process. Therefore, it is possible to suppress roughening of the structure of the glass composition due to zinc oxide. However, when the content of copper oxide exceeds 7 wt%, crystal precipitation phenomenon in the produced glass fiber tends to increase, which is disadvantageous for subsequent use.
一部の実施例においは、前記ガラス組成物の重量パーセント１００ｗｔ％に対して、添加された酸化銅の含有量は０．５ｗｔ％～７ｗｔ％の範囲にあるが、これに限定されるものではなく、該酸化銅の含有量が４ｗｔ％～７ｗｔ％の範囲にあり、該酸化銅と酸化亜鉛の含有量の合計が４．５ｗｔ％～７ｗｔ％の範囲にあることが好ましい。尚、他の実施例においては、該酸化マグネシウムと酸化亜鉛と酸化銅の含有量の合計が１２ｗｔ％～１５ｗｔ％の範囲にあってもよい。 In some embodiments, the content of added copper oxide is in the range of 0.5 wt% to 7 wt% based on 100 wt% of the glass composition, but is not limited thereto. Preferably, the copper oxide content is in the range of 4 wt% to 7 wt%, and the total content of the copper oxide and zinc oxide is in the range of 4.5 wt% to 7 wt%. In other embodiments, the total content of magnesium oxide, zinc oxide, and copper oxide may be in the range of 12 wt% to 15 wt%.
本実施例においては、前記ガラス組成物の重量パーセント１００ｗｔ％に対して、該ドーパントの含有量が１．２ｗｔ％以下であり、該ドーパントは、酸化ナトリウム、酸化カリウム、酸化鉄及び二酸化チタンのうちの少なくとも一種を含有しており、該ドーパントがもたらす利点の一部は、ガラス組成物以外の微量成分に由来する。 In this example, the content of the dopant is 1.2 wt% or less with respect to 100 wt% of the glass composition, and the dopant is one of sodium oxide, potassium oxide, iron oxide, and titanium dioxide. Some of the benefits provided by the dopant are derived from trace components other than the glass composition.
前記酸化ナトリウム、酸化カリウムなどのアルカリ性酸化物は、本発明のガラス組成物の耐酸性を向上させると共に、当該ガラス組成物の融点を下げ、ガラス繊維の製造に役立つが、これらアルカリ性酸化物の含有量が多すぎると、生成されたガラス繊維の化学的安定性が低下すると共に、当該ガラス繊維の電気絶縁性及び機械的強度も低下する。前記酸化鉄は、ガラス組成物の製造における溶融、紡糸などの工程においての安定性を向上させることができるが、酸化鉄の含有量が多すぎると、当該ガラス組成物の製造において温度ムラが発生する。前記二酸化チタンは、ガラス組成物の機械的強度を高めるのに役立つが、含有量が多すぎると、当該ガラス組成物の製造において結晶析出現象を起こしやすい。 The alkaline oxides such as sodium oxide and potassium oxide improve the acid resistance of the glass composition of the present invention, lower the melting point of the glass composition, and are useful for manufacturing glass fibers. If the amount is too large, the chemical stability of the glass fibers produced will decrease, as well as the electrical insulation properties and mechanical strength of the glass fibers. The iron oxide can improve the stability in processes such as melting and spinning in the production of glass compositions, but if the content of iron oxide is too large, temperature unevenness will occur in the production of the glass compositions. do. The titanium dioxide is useful for increasing the mechanical strength of the glass composition, but if the content is too large, crystal precipitation may easily occur during the production of the glass composition.
以下、本発明の各実施形態に係るガラス組成物について、第１～第９実施例を用いて説明する。また、後述する第１～第９実施例及び第１、第２比較例のガラス組成物からなるガラス繊維の熱膨張係数を表１にまとめた。 Hereinafter, glass compositions according to each embodiment of the present invention will be explained using Examples 1 to 9. In addition, Table 1 summarizes the thermal expansion coefficients of glass fibers made of glass compositions of the first to ninth examples and the first and second comparative examples, which will be described later.
＜熱膨張係数の測定方法＞
本発明の実施例においては、熱膨張係数の測定を熱機械分析装置（日立製作所製）により行い°Ｃ、その測定方法では、まず、ガラス組成物を溶融して、板状ガラス（寸法約０．５ｃｍ＊０．５ｃｍ＊２ｃｍ）を得て、その後、該板状ガラスを１０°Ｃ／ｍｉｎの温度上昇速度で加熱し、５０°Ｃ～２００°Ｃの温度範囲で当該板状ガラスの伸び量を測定して、平均熱膨張係数を算出する。
<Measurement method of thermal expansion coefficient>
In the examples of the present invention, the coefficient of thermal expansion was measured using a thermomechanical analyzer (manufactured by Hitachi, Ltd.) at °C. .5cm*0.5cm*2cm), and then the plate glass was heated at a temperature increase rate of 10°C/min, and the plate glass was elongated in the temperature range of 50°C to 200°C. The average coefficient of thermal expansion is calculated by measuring the amount.
＜第１実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５９．４ｗｔ％の酸化ケイ素と、約１９．１ｗｔ％の酸化アルミニウムと、約６．５ｗｔ％の酸化ホウ素と、約４．４ｗｔ％の酸化亜鉛と、約０．４ｗｔ％の酸化カルシウムと、約９．１ｗｔ％の酸化マグネシウムと、約０．１ｗｔ％の酸化銅と、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６４ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<First example>
In this example, the weight percentage of the glass composition is 100 wt %, and the components have the following weight percentages: about 59.4 wt % silicon oxide, about 19.1 wt % aluminum oxide, and about 6. 5 wt% boron oxide, about 4.4 wt% zinc oxide, about 0.4 wt% calcium oxide, about 9.1 wt% magnesium oxide, about 0.1 wt% copper oxide, about 1. 0 wt% of said dopants (0.03 wt% sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ) and 0.64 wt% titanium dioxide (TiO 2 )).
上述した第１実施例のガラス組成物を十分に混合した後、１５００℃～１５５０℃の温度で溶融し、その後、成形、裁断、研磨などの工程を経て、該第１実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第１実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．９０ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 After thoroughly mixing the glass composition of the first example described above, it is melted at a temperature of 1500°C to 1550°C, and then undergoes processes such as molding, cutting, and polishing to obtain the glass composition of the first example. Obtain a plate glass consisting of. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of this first example was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 2.90 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
尚、ガラス組成物に混合、溶融、紡糸などの工程を施すことにより得る、板状ガラスまたはガラス繊維に関する製造条件パラメータ及び具体的な製造工程は、当業者にとって周知技術であり、また、成分によっては、関連する製造条件パラメータが若干異なる場合があるが、これらの製造条件パラメータの調整は、当業者にとって周知の技術であるので、ここでその詳細な説明は省略する。 The manufacturing condition parameters and specific manufacturing steps regarding plate glass or glass fiber obtained by subjecting a glass composition to processes such as mixing, melting, and spinning are well known to those skilled in the art, and may vary depending on the components. The related manufacturing condition parameters may be slightly different, but since adjustment of these manufacturing condition parameters is a well-known technique to those skilled in the art, a detailed explanation thereof will be omitted here.
＜第２実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５６．３ｗｔ％の酸化ケイ素と、約１９．２ｗｔ％の酸化アルミニウムと、約１０．０ｗｔ％の酸化ホウ素と、約６．５ｗｔ％の酸化亜鉛と、約０．２ｗｔ％の酸化カルシウムと、約６．２ｗｔ％の酸化マグネシウムと、約０．５ｗｔ％の酸化銅と、約１．１ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３４ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．７ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Second example>
In this example, the weight percent of the glass composition is 100 wt.%, and the components have the following weight percents: about 56.3 wt.% silicon oxide, about 19.2 wt.% aluminum oxide, and about 10.3 wt.% silicon oxide. 0 wt% boron oxide, about 6.5 wt% zinc oxide, about 0.2 wt% calcium oxide, about 6.2 wt% magnesium oxide, about 0.5 wt% copper oxide, about 1. 1 wt% of said dopants (0.03 wt% sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.34 wt% iron oxide (Fe 2 O 3 ) and 0.7 wt% titanium dioxide (TiO 2 )).
上述した第２実施例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第２実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第２実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．６４ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 A sheet glass made of the glass composition of the second example is obtained by sequentially subjecting the glass composition of the second example to processes such as mixing and melting. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of this second example was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 2.64 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
＜第３実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５６．４ｗｔ％の酸化ケイ素と、約１９．２ｗｔ％の酸化アルミニウムと、約１１．０ｗｔ％の酸化ホウ素と、約６．５ｗｔ％の酸化亜鉛と、約０．２ｗｔ％の酸化カルシウムと、約５．２ｗｔ％の酸化マグネシウムと、約０．５ｗｔ％の酸化銅と、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６４ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Third Example>
In this example, the weight percentage of the glass composition is 100 wt%, and the following weight percentages are used: approximately 56.4 wt% silicon oxide, approximately 19.2 wt% aluminum oxide, and approximately 11.4 wt% silicon oxide. 0 wt% boron oxide, about 6.5 wt% zinc oxide, about 0.2 wt% calcium oxide, about 5.2 wt% magnesium oxide, about 0.5 wt% copper oxide, about 1. 0 wt% of said dopants (0.03 wt% sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ) and 0.64 wt% titanium dioxide (TiO 2 )).
上述した第３実施例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第３実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第３実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．７０ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 A sheet glass made of the glass composition of the third example is obtained by sequentially subjecting the glass composition of the third example to processes such as mixing and melting. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of this third example was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 2.70 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
＜第４実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５９．４ｗｔ％の酸化ケイ素と、約１９．１ｗｔ％の酸化アルミニウムと、約６．５ｗｔ％の酸化ホウ素と、約３．５ｗｔ％の酸化亜鉛と、約０．４ｗｔ％の酸化カルシウムと、約９．１ｗｔ％の酸化マグネシウムと、約１．０ｗｔ％の酸化銅と、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６４ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Fourth Example>
In this example, the weight percentage of the glass composition is 100 wt %, and the components have the following weight percentages: about 59.4 wt % silicon oxide, about 19.1 wt % aluminum oxide, and about 6. 5 wt% boron oxide, about 3.5 wt% zinc oxide, about 0.4 wt% calcium oxide, about 9.1 wt% magnesium oxide, about 1.0 wt% copper oxide, about 1. 0 wt% of said dopants (0.03 wt% sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ) and 0.64 wt% titanium dioxide (TiO 2 )).
上述した第４実施例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第４実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第４実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．８２ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 By sequentially subjecting the glass composition of the fourth example to processes such as mixing and melting, a plate glass made of the glass composition of the fourth example is obtained. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of this fourth example was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 2.82 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
＜第５実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５９．４ｗｔ％の酸化ケイ素と、約１９．１ｗｔ％の酸化アルミニウムと、約６．５ｗｔ％の酸化ホウ素と、約２．５ｗｔ％の酸化亜鉛と、約０．４ｗｔ％の酸化カルシウムと、約９．１ｗｔ％の酸化マグネシウムと、約２．０ｗｔ％の酸化銅と、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６４ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Fifth example>
In this example, the weight percentage of the glass composition is 100 wt %, and the components have the following weight percentages: about 59.4 wt % silicon oxide, about 19.1 wt % aluminum oxide, and about 6. 5 wt% boron oxide, about 2.5 wt% zinc oxide, about 0.4 wt% calcium oxide, about 9.1 wt% magnesium oxide, about 2.0 wt% copper oxide, about 1. 0 wt% of said dopants (0.03 wt% sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ) and 0.64 wt% titanium dioxide (TiO 2 )).
上述した第５実施例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第５実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第５実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．８０ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 A sheet glass made of the glass composition of the fifth example is obtained by sequentially subjecting the glass composition of the fifth example to processes such as mixing and melting. Next, using the plate glass as a standard measurement sample, the thermal expansion coefficient of the plate glass made of the glass composition of the fifth example was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 2.80 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
＜第６実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５９．４ｗｔ％の酸化ケイ素と、約１９．１ｗｔ％の酸化アルミニウムと、約６．５ｗｔ％の酸化ホウ素と、約０．４ｗｔ％の酸化カルシウムと、約９．１ｗｔ％の酸化マグネシウムと、約４．５ｗｔ％の酸化銅と、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６４ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Sixth Example>
In this example, the weight percentage of the glass composition is 100 wt %, and the components have the following weight percentages: about 59.4 wt % silicon oxide, about 19.1 wt % aluminum oxide, and about 6. 5 wt% boron oxide, about 0.4 wt% calcium oxide, about 9.1 wt% magnesium oxide, about 4.5 wt% copper oxide, and about 1.0 wt% of the dopant (0.03 wt% of sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ) and 0.64 wt% titanium dioxide (TiO 2 )). contains.
上述した第６実施例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第６実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第６実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．６５ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 By sequentially subjecting the glass composition of the above-mentioned sixth example to processes such as mixing and melting, a plate glass made of the glass composition of the sixth example is obtained. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of Example 6 was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 2.65 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
＜第７実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５９．４ｗｔ％の酸化ケイ素と、約１９．２ｗｔ％の酸化アルミニウムと、約６．５ｗｔ％の酸化ホウ素と、約０．３ｗｔ％の酸化カルシウムと、約７．１ｗｔ％の酸化マグネシウムと、約６．５ｗｔ％の酸化銅と、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６４ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Seventh Example>
In this example, the weight percentage of the glass composition is 100 wt %, and the following weight percentages are used: approximately 59.4 wt % silicon oxide, approximately 19.2 wt % aluminum oxide, and approximately 6.5 wt % silicon oxide. 5 wt% boron oxide, about 0.3 wt% calcium oxide, about 7.1 wt% magnesium oxide, about 6.5 wt% copper oxide, and about 1.0 wt% of the dopant (0.03 wt% of sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ) and 0.64 wt% titanium dioxide (TiO 2 )). contains.
上述した第７実施例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第７実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第７実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．３９ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 A plate glass made of the glass composition of the seventh example is obtained by sequentially subjecting the glass composition of the seventh example to processes such as mixing and melting. Next, using the plate glass as a standard measurement sample, the thermal expansion coefficient of the plate glass made of the glass composition of Example 7 was measured according to the method for measuring the coefficient of thermal expansion described above, and it was 2.39 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
＜第８実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５９．４ｗｔ％の酸化ケイ素と、約２０．８ｗｔ％の酸化アルミニウムと、約６．５ｗｔ％の酸化ホウ素と、約０．２ｗｔ％の酸化カルシウムと、約５．５ｗｔ％の酸化マグネシウムと、約６．５ｗｔ％の酸化銅と、約１．１ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３４ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．７ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Eighth Example>
In this example, the weight percentage of the glass composition is 100 wt %, and the following weight percentages are used: approximately 59.4 wt % silicon oxide, approximately 20.8 wt % aluminum oxide, and approximately 6.5 wt % silicon oxide. 5 wt% boron oxide, about 0.2 wt% calcium oxide, about 5.5 wt% magnesium oxide, about 6.5 wt% copper oxide, and about 1.1 wt% of the dopant (0.03 wt% of sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.34 wt% iron oxide (Fe 2 O 3 ) and 0.7 wt% titanium dioxide (TiO 2 )). contains.
上述した第８実施例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第８実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第８実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．１８ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 A sheet glass made of the glass composition of the eighth example is obtained by sequentially subjecting the glass composition of the eighth example to processes such as mixing and melting. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of the eighth example was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 2.18 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
＜第９実施例＞
本実施例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約５９．４ｗｔ％の酸化ケイ素と、約１８．７ｗｔ％の酸化アルミニウムと、約６．５ｗｔ％の酸化ホウ素と、約０．３ｗｔ％の酸化カルシウムと、約７．１ｗｔ％の酸化マグネシウムと、約７．０ｗｔ％の酸化銅と、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０３ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６４ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Ninth Example>
In this example, the weight percentage of the glass composition is 100 wt%, and the following weight percentages are used: approximately 59.4 wt% silicon oxide, approximately 18.7 wt% aluminum oxide, and approximately 6.5 wt% silicon oxide. 5 wt% boron oxide, about 0.3 wt% calcium oxide, about 7.1 wt% magnesium oxide, about 7.0 wt% copper oxide, and about 1.0 wt% of the dopant (0.03 wt% of sodium oxide (Na 2 O), 0.03 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ) and 0.64 wt% titanium dioxide (TiO 2 )). contains.
上述した第９実施例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第９実施例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第９実施例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、２．３３ｐｐｍ／℃の熱膨張係数を得て、さらに、その後、混合、溶融、紡糸などの工程を経て、低熱膨張係数を持つガラス繊維を得る。 A sheet glass made of the glass composition of the ninth example is obtained by sequentially subjecting the glass composition of the ninth example to processes such as mixing and melting. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of this ninth example was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 2.33 ppm/°C. After that, glass fibers with a low coefficient of thermal expansion are obtained through processes such as mixing, melting, and spinning.
＜第１比較例＞
本比較例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約６０．０ｗｔ％の酸化ケイ素と、約２０．０ｗｔ％の酸化アルミニウムと、約５．０ｗｔ％の酸化ホウ素と、約３．０ｗｔ％の酸化カルシウムと、約１１．０ｗｔ％の酸化マグネシウムと、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０２ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６５ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<First comparative example>
In this comparative example, assuming the weight percentage of the glass composition to be 100 wt%, components having the following weight percentages were used: approximately 60.0 wt% silicon oxide, approximately 20.0 wt% aluminum oxide, and approximately 5.0 wt%. 0 wt% boron oxide, about 3.0 wt% calcium oxide, about 11.0 wt% magnesium oxide, and about 1.0 wt% of the dopant (0.03 wt% sodium oxide ( Na2O ), 0 It contains 0.02 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ), and 0.65 wt% titanium dioxide (TiO 2 ).
上述した第１比較例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第１比較例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第１比較例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、３．３４ｐｐｍ／℃の熱膨張係数を得た。 A sheet glass made of the glass composition of the first comparative example is obtained by sequentially subjecting the glass composition of the first comparative example to processes such as mixing and melting. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of this first comparative example was measured according to the method for measuring the thermal expansion coefficient described above, and it was 3.34 ppm/°C. The coefficient of thermal expansion was obtained.
＜第２比較例＞
本比較例においては、ガラス組成物の重量パーセントを１００ｗｔ％として、次の重量パーセントを有する成分、つまり、約６０．０ｗｔ％の酸化ケイ素と、約２０．０ｗｔ％の酸化アルミニウムと、約１０．０ｗｔ％の酸化ホウ素と、約６．０ｗｔ％の酸化カルシウムと、約３．０ｗｔ％の酸化マグネシウムと、約１．０ｗｔ％の前記ドーパント（０．０３ｗｔ％の酸化ナトリウム（Ｎａ２Ｏ）、０．０２ｗｔ％の酸化カリウム（Ｋ２Ｏ）、０．３ｗｔ％の酸化鉄（Ｆｅ２Ｏ３）及び０．６５ｗｔ％の二酸化チタン（ＴｉＯ２））とを含有する。
<Second comparative example>
In this comparative example, assuming the weight percentage of the glass composition to be 100 wt%, components having the following weight percentages were used: approximately 60.0 wt% silicon oxide, approximately 20.0 wt% aluminum oxide, and approximately 10.0 wt% silicon oxide. 0 wt% boron oxide, about 6.0 wt% calcium oxide, about 3.0 wt% magnesium oxide, and about 1.0 wt% of the dopant (0.03 wt% sodium oxide ( Na2O ), 0 wt% It contains 0.02 wt% potassium oxide (K 2 O), 0.3 wt% iron oxide (Fe 2 O 3 ), and 0.65 wt% titanium dioxide (TiO 2 ).
上述した第２比較例のガラス組成物に順次混合、溶融などの工程を施すことにより、該第２比較例のガラス組成物からなる板状ガラスを得る。次に、当該板状ガラスを標準測定試料とし、前述の熱膨張係数の測定方法に従って、この第２比較例のガラス組成物からなる板状ガラスの熱膨張係数を測定し、３．１１ｐｐｍ／℃の熱膨張係数を得た。 By sequentially subjecting the glass composition of the second comparative example to processes such as mixing and melting, a plate glass made of the glass composition of the second comparative example is obtained. Next, using the sheet glass as a standard measurement sample, the thermal expansion coefficient of the sheet glass made of the glass composition of this second comparative example was measured according to the method for measuring the thermal expansion coefficient described above, and it was found to be 3.11 ppm/°C. The coefficient of thermal expansion was obtained.
表１からも明らかなように、酸化銅及び酸化亜鉛を添加することにより、本発明の第１～第９実施例のガラス組成物の熱膨張係数は、第１、第２比較例に比べて、３ｐｐｍ／℃以下に低減することができる。また、ガラス組成物中の酸化銅の含有量が４．５ｗｔ％以上であり、且つ、酸化亜鉛を含まない場合（第６～第９実施例）には、当該ガラス繊維の熱膨張係数をさらに２．６５ｐｐｍ／℃以下に低減することができる。さらに、酸化銅の含有量を６．５ｗｔ％～７．０ｗｔ％（第７～第９実施例）にさらに増加させると、当該ガラス組成物からなる板状ガラスの熱膨張係数が２．４ｐｐｍ／℃以下に低減される。 As is clear from Table 1, by adding copper oxide and zinc oxide, the thermal expansion coefficients of the glass compositions of the first to ninth examples of the present invention are higher than those of the first and second comparative examples. , can be reduced to 3 ppm/°C or less. In addition, when the content of copper oxide in the glass composition is 4.5 wt% or more and does not contain zinc oxide (Examples 6 to 9), the coefficient of thermal expansion of the glass fiber is further increased. It can be reduced to 2.65 ppm/°C or less. Furthermore, when the content of copper oxide is further increased to 6.5 wt% to 7.0 wt% (7th to 9th examples), the coefficient of thermal expansion of the sheet glass made of the glass composition is 2.4 ppm/ reduced to below ℃.
詳しく説明すると、第１実施例、第４～第６実施例のガラス組成物と比較すると、他の成分の含有量が近い場合、酸化亜鉛の含有量が減少し、酸化銅の含有量が増加することにより、製成されたガラス繊維の熱膨張係数が徐々に低減し、酸化亜鉛の含有量を０ｗｔ％に低減し、且つ酸化銅の含有量を４．５ｗｔ％（第６実施例）に増加させると、製成されたガラス繊維の熱膨張係数が２．６５ｐｐｍ／℃に低減する。さらに、第６～第９実施例のガラス組成物と比較すると、酸化亜鉛を含まずに、他の成分の含有量がほぼ同じである場合、酸化マグネシウムと酸化カルシウムの含有量を適量に減らして、酸化銅の含有量を７ｗｔ％までに増加させることにより、当該ガラス繊維の熱膨張係数を２．４ｐｐｍ／℃以下（第７～第９実施例）に低減させることができることが分かった。 To explain in detail, compared to the glass compositions of the first example and the fourth to sixth examples, when the contents of other components are similar, the content of zinc oxide decreases and the content of copper oxide increases. By doing so, the thermal expansion coefficient of the produced glass fiber was gradually reduced, the content of zinc oxide was reduced to 0 wt%, and the content of copper oxide was reduced to 4.5 wt% (6th example). When increased, the coefficient of thermal expansion of the glass fiber produced is reduced to 2.65 ppm/°C. Furthermore, compared to the glass compositions of Examples 6 to 9, when the contents of other components are almost the same without containing zinc oxide, the contents of magnesium oxide and calcium oxide are reduced to appropriate amounts. It was found that by increasing the content of copper oxide to 7 wt%, the coefficient of thermal expansion of the glass fiber could be reduced to 2.4 ppm/°C or less (Examples 7 to 9).
要約すると、本發明低熱膨張係数を持つガラス組成物は、酸化銅の含有量を増加させ、酸化亜鉛の含有量を減少させ、且つ、酸化マグネシウム及び酸化カルシウムの含有量を適量に減少させることにより、本発明に係るガラス組成物からなるガラス繊維の熱膨張係数を３ｐｐｍ／℃以下に低減することができることから、本発明に係るガラス繊維を半導体の製造や電子産業に広く適用することが可能となるので、本発明の目的を確実に達成することができる。 In summary, the present glass composition with a low thermal expansion coefficient can be obtained by increasing the content of copper oxide, decreasing the content of zinc oxide, and reducing the content of magnesium oxide and calcium oxide by appropriate amounts. Since the coefficient of thermal expansion of the glass fiber made from the glass composition according to the present invention can be reduced to 3 ppm/°C or less, the glass fiber according to the present invention can be widely applied to semiconductor manufacturing and the electronic industry. Therefore, the object of the present invention can be achieved reliably.
以上の説明は、本発明の好適な実施形態に過ぎず、本発明に対して何ら限定を行うものではない。本発明について、比較的好適な実施形態をもって上記のとおり説明を行ったが、これは本発明を限定するものではなく、すべての当業者が、本発明の技術構想を逸脱しない範囲において、本発明の技術の本質に基づいて上記の実施形態に対して行ういかなる簡単な修正、変更及び修飾も、依然としてすべて本発明の技術構想の範囲に含まれる。
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. Although the present invention has been described above using relatively preferred embodiments, this does not limit the present invention, and anyone skilled in the art will understand that the present invention Any simple modifications, changes and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical concept of the present invention.
Claims (13)
該ガラス組成物の重量パーセント１００ｗｔ％に対して、
該酸化ケイ素の含有量は５５ｗｔ％～６３ｗｔ％の範囲にあり、
該酸化アルミニウムの含有量は１５ｗｔ％～２２ｗｔ％の範囲にあり、
該酸化ホウ素の含有量は６ｗｔ％～１３ｗｔ％の範囲にあり、
該酸化マグネシウムの含有量は５ｗｔ％～１４ｗｔ％の範囲にあり、
該酸化カルシウムの含有量は０．１ｗｔ％～０．４ｗｔ％の範囲にあり、
該酸化銅の含有量は０．０３ｗｔ％～７ｗｔ％の範囲にあることを特徴とする低熱膨張係数を持つガラス組成物。 A glass composition with a low coefficient of thermal expansion, comprising silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), boron oxide (B 2 O 3 ), magnesium oxide (MgO), calcium oxide (CaO) and oxide Contains copper (CuO),
With respect to 100 wt% of the glass composition,
The content of silicon oxide is in the range of 55 wt% to 63 wt%,
The content of aluminum oxide is in the range of 15 wt% to 22 wt%,
The content of the boron oxide is in the range of 6 wt% to 13 wt%,
The content of the magnesium oxide is in the range of 5 wt% to 14 wt%,
The content of calcium oxide is in the range of 0.1 wt% to 0.4 wt%,
A glass composition having a low coefficient of thermal expansion, characterized in that the copper oxide content is in the range of 0.03 wt% to 7 wt%.
The product according to claim 12, wherein the product is a printed circuit board, an IC chip mounting board, or a radar dome.
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